Catalytic halo-substitution of saturated organic compounds



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William 'E. Vaughan and Frederick. F. Bust, Berkeley, Calif asslgnors to Shell Development Company, San of Delaware Calif... a corporation No, Drawing. Application September 1, 1942, Serial No. 45am 130mm. (or. 260-602) The present invention relates to the halo-substitution of. saturated organic compounds, and more particularly pertains to a catalytic process for eflecting the halogenation, via substitution, of saturated aliphatic and alicyclic hydrocarbons or of their partially halogenated derivatives. The present application is a continuation-in-part of our co-pending application, Serial No. 293,256, filed September 2, 1939, now Patent No. 2,299,441.

The halogenation of saturated organic compounds, such as saturated aliphatic and alicyclic hydrocarbons, as well as partially halogenated derivatives thereof, is well known. These hydrocarbons react with the halogen, such as chlorine, bromine or iodine, to formproducts of halosubstitution, 1. e. compounds in which one or more halogen atoms take the places of hydrogen atoms of the compound subjected to halogenation. It is also known that such halo-substitution reaction between a halogen and a saturated organic coinpound of the class described may be effected by subjecting the mixture to elevatedtemperatures which favor the halo-substitution reaction, these temperatures, however, being below those at which substantial degradation and/or decomposition of the reactants and/or products of reaction occurs.

Generally, the halo-substitution reaction between saturated aliphatic and/or alicyclic organic compounds and the halogen is effected by mixing the reactants, and then subjecting the mixture thus formed to the desired reaction temperature. As an alternative, the. saturated aliphatic or alicyclic compounds to b halogenated, or the partially halogenated derivatives thereof to be subjected to further halo-substitution, are heated and then mixed with a heated or unheated halogen, thereby effecting the desired reaction; or the heated halogen may be mixed with the unheated or less heated organic compound to be halogenated. Since the halo-substitution reaction is exothermic in character, it is unnecessary to preheat a reactant or the reactants to the optimum reaction temperature. The desired or necessary temperature for the effecting of such thermal halo-substitution reactions will naturally vary with the nature of the saturated organic reactant, the character of the halogen employed, the type of reactor, the presence or absence of a diluent, the employed pressure, space velocity, etc.

' Generally, it may be stated that the optimum temperatures for the thermal halo-substitution of described class of saturated organic compounds the upper limit being controlled and determined by the degree of degradation or decomposition of the reactants and/or reaction products obtained.

. The use of such relatively high temperatures is frequently undesirable because of the relatively high initial cost of plant installation and the cost of its maintenance and operation. Also, due to the above-mentioned exothermic character of the halo-substitution reactions, it is frequently diflicult to control these high temperature reactions, which usually tend to cause excessive decomposition of the reactants, formation of carbon and tar, etc. Furthermore, the aforementioned high temperature reactions necessitate the preheating of the reactants. Since halogen is highly reactive especially at the relatively high temperatures ordinarily employed for the thermal halosubstitution of the saturated hydrocarbons of the class mentioned and described herein, it is often necessary to employ preheaters, mixers and/ or reactors which are constructed of or at least lined with special materials, such as hard carbon, Monel metal, Hastelloy, andthe like, which are substantially inert to and unattached by the halogen even at the elevated temperatures em- 7 via substitution.

will lie between about 225 C. and about 700 (3.,

It is therefore the general object of the present invention to avoid the above and other. defects and dificulties, and to provide an. improved process for the halogenation, via substitution, of saturated organic compounds, and particularly of saturated aliphatic and alicyciic hydrocarbons and of their partially halogenated derivatives. It is a further object to provide'an improved process wherein saturated organic compounds of the class described herein may be effectively and economically'reacted with a free halogen, or with a reactant capable of yielding a free halogen under the operating conditions employed, at relatively lower temperature which could not be employed heretofore for the production of products of halosubstitution. A still further object is to provide a process wherein the above-outlined saturated organic compounds may be eifectively halogenated, via substitution, at temperatures below about 225 C., i. e. below the lower temperature limit at which said compounds couldbe previously thermallyhalogenated in the dark.

The term "free radical, as employed herein and in the appended claims, refers to an organic compound in which not all of the vaiences are satisfied (see Hackhs Chemical Dictionary, 2nd ed., page 397) These free radicals are electrically neutral molecules possessing an unpaired electron and exhibiting an unsaturated behavior. These properties distinguish the free radicals from ions (such as those obtained by the ionization of certain salts or in electric discharges in ases).

It has also been discovered that when organic peroxides are employed as the catalyst, the free radicals produced and existing as such during the halogenation reaction will catalyze the reaction between the halogens and the saturated organic compounds of the outlined class, so that the halo-substituted reaction may be effectively and efiiciently realized at relatively low temperatures. Thus, as will be brought out more fully hereinbelow, by using organic peroxides capable of yielding free radicals under the operating con ditions as the catalyst, it is now possible to effect the reaction between a halogen and a saturated organic compound to produce high yields of products of halogenation, via substitution, even at temperatures at which no or substantially no halo-substitution could be realized if the reaction were to be attempted at such temperatures Without the use of the catalyst. It was further discovered that the presence of the organic peroxides (which yield free radicals under the operating conditions) permits the effecting of the above halo-substitution reactions both in the liquid and the vapor phases and at temperatures eiiectively below 200 C. or 225 C., which is usually the minimum temperature range for the non-catalytic, thermal halogenation, via substitution, of the outlined class of saturated aliphatic and allcyclic hydrocarbons, and of their partially halogenated derivatives.

Representative saturated organic compounds of the class which may be halo-substituted in accordance with the process of the invention are the saturated aliphatic hydrocarbons, such as ethane, propane, n-butane, isobutane, n-pentane, isopentane, and the straight and branched-chain hexanes, heptanes, octanes, nonanes. and the like; the alicyclic hydrocarbons, as cyclopropane, cyclobutane, cyclopentane, cyclohexane, the higher homologues thereof, and. the alkylated cycloparafiins, such as methyl cyclopentane, methyl cyclohexane, and the like; and the partially halo-substituted normal and branchedchain saturated aliphatic and alicyclic hydrocarbons, such as ethyl chloride, dichlor-ethane, l-chloropropane, Z-chloropropane, 1.1-dichloropropane, 1,2-dichloropropane, 1.3-dichlropropane, dibromopropanes. monochlorobutanes, dichlorobutanes, monobromobutanes, dibromobutanes, 'monochlorcyclopentane, and the like. and their homologues and analogues. The saturated aliphatic or alicyclic compound may also be linked to one or more aromatic radicals. 'For example, compounds which may '-be treated in accordance with the process of the present invention include phenyl alkyl hydrocarbons and products of their partial halo-substitution. Also. saturated aliphatic and/or alicyclic acids,

ketones, alcohols, esters, etc., fall within the class maintained in the halogenation reaction zone,

eflect the halogenation of the saturated organic compounds at temperatures below about 200 C. and even at room temperatures or below and in the liquid phase. Such low temperatures are ,wholly ineffective or, at least, highly inefficient for the non-catalytic halo-substitution reactions in accordance with the previously known processes.

It was stated above that organic peroxides will catalyze or promote the halo-substitution reaction in accordance with the process of the present invention. Without any intention of being limited by the compounds enumerated herein, it may be stated that the following are representative examples of organic peroxides which may be used: the aliphatic peroxides, such as diethyl peroxide, peracetic acid, oxy-heptyl hydroperoxide, mon'o-oxy-dimethyl peroxide, dioxy-methyl peroxide, mesityloxide peroxide, lauroyl peroxide, and the like, and their homologues; the aromatic peroxides, as benzoyl peroxide, perbenzoic acid, and the like, and their homologues; the naturally occurring peroxides, e. g. ascaridole; and the ether peroxides, such as di-isopropyl' ether peroxide.

The optimum temperatures to be employed for the halogenation, via substitution, according to the present invention depend on a number of variables, such as the specific saturated aliphatic or alicyclic organic compound to be halogenated and the halogen employed, as well as on the specific organic peroxide employed as the catalyst. The temperature must be such that the organic peroxide is decomposed or cleaved to liberate the organic free radicals which catalyze the halo-substitution reaction. Since such temperatures will be difierent from the various organic peroxides which comprise the halogenation promoting agents or catalysts of the present invention, it is impossible to specify any definite optimum temperatures. However, it may be stated that, when an organic peroxide is used as the catalyst, it is possible to effect the halogenation, via substitution, of the saturated aliphatic and/or alicyclic hydrocarbons, and of their partially halogenated derivatives, at temperatures substantially below those necessary for such halo-substitution when the reaction is attempted without the use of the catalyst. In fact, the present invention permits the efiecting of the halo-substitution reaction not only in the vapor phase, but-also in the liquid phase and at or below room temperatures. In this connection it must be noted that some of the organic peroxides may not be cleaved or decomposed to yield the free radicals until or unless subjected to relatively high temperatures. Such compounds, therefore, may not be useful as halogenation promoting catalysts, since the high temperatures necessary for their cleavage will also initiate the halogenation reaction by activating the halogen employed and thus initiating the reaction chain mechanism. It is possible, however, that the halogen will react with such organic peroxides to eflect the cleavage thereof and the liberation of the free radicals under the operating conditions, or that the efl'ect of the activated halogen and of the free radicals formed will be cumulative. thereby increasing the rate of halo-substitution obtained.

' The invention is illustrated by the following examples which are presented herein for the purpose of showing the advantages derived from 100 cc. of oxygen-free and peroxide-free normal heptane were introduced into a blackened flask which was maintained in an ice-water bath. Chlorine was conveyed through the normal heptane for a period of ten minutes at a rate of 50 cc. per minute. Both light and oxygen were rigidly excluded from the system. At the end of the ten minute period the solution was found,

to be intensely colored with unreacted chlorine. No hydrogen chloride was found, thus clearly indicating that no halo-substitution occurred.

Example II The apparatus was identical with the one employed in the above-described run. The blackened flask in this case, however, contained 2 cc. of ascaridole (which is a naturally occurring organic peroxide) in addition to the 100 cc. of the oxygen-free and peroxide-free normal heptane. As in the above-described run, chlorine was conveyed through the normal heptane at a rate of 50 cc. per minute for a period of ten minutes. Also, light and oxygen were rigidly excluded from the system, the normal heptane being furthermore maintained in a liquid state by means of an icewater bath surrounding the flask. At the end of the ten minute period, the liquid mixture in the flask was analyzed. No unreacted chlorine was found; the liquid mixture furthermore was found to contain hydrogen chloride, thus indicating that chlor-substitution did occur. It is to be noted that the ascaridole was employed in an amount equal to 1.3 mol per cent as calculated on the basis of the mixture subjected to halogenation.

Example I]! Two identical blackened flasks were placed into a bath containing ice and water. Both light and oxygen were rigidly excluded from the system, One hundred (100) cc. of oxygen-free and peroxide-free toluene were introduced into the first flask, while 100 cc. of the same oxygen-free chloride in the run in which benzoyl peroxide was present, thus clearly proving that the chlorlsubstitution reaction was promoted by this catayst.

The above examples bring out the advantages derived from eflecting the halo-substitution reaction according to the present invention. Thus, the introduction of even very small quantities of organic peroxides (which will yield free radicals under the-halogenating conditions) permits the realization of the halo-substitution of saturated aliphatic or alicyclic organic compoundseven in the liquid phase, in the absence of actinic radiations, and at temperatures at which no, or at least substantially no, halo-substitution occurs when a catalyst is not employed. As stated, very small quantities of the organic peroxide are sufficient to effect substantially complete halo-substitution. For instance, it is possible to effect the reaction with quantities of the above-described catalyst ranging from very small percenta'ges of the order of about 0.1, mol per cent to about 4 or 5 mol per cent. However, still higher or lower percentages may be found desirable and even advantageous under certain conditions of operation, depending, for instance, on whether the reaction is effected in the liquid phase and at relatively very low temperatures, or in the vapor phase and at relatively higher temperatures.

Although the invention has been described with particular reference to the chlorination of saturated aliphatic hydrocarbons, it is to be understood that saturated alicycli-c hydrocarbons, other saturated organic compounds, as well as the partially halogenated derivatives of these organic compounds may be halogenated, i. e. subjected to chlorination, bromination and/ or iodination, via substitution, in accordance with the process of this invention. Also, instead of employing a free halogen per se, any of the known free halogen yielding substances, which are capable of liberating a free halogen under the conditions existing in the reaction system, may also be used. As 45 such, reference is made to sulfuryl chloride, ni-

trosyl chloride, etc.

It will be evident to those skilled in the art that the invention may be executed ina batch, intermittent or continuous manner. Generally, it is preferable to employ an amount of halogen not in excess of that theoretically required to react with all of the saturated aliphatic and/or alicyclic organic compound to be halogenated. The presence of an excess of the halogen is usually avoided since such excesses are conducive to the formation of undesirable highly halogenated products, while an excess of the compound to be halogenated is often desirable in the reaction zone.

The reaction may be effected at any suitable pressure. Generally, the halo-substitution reaction according to the present invention may be effected at atmospheric pressures. However, somewhat higher or lower pressures may also be employed. Also, the reaction may be effected in the vapor or liquid phases, or in a vapor-liquid phase, i. e. while one or both of the reactants and/or the reaction product are partially in a liquid and partially in a vapor state. In some instances, and this is particularly true of the vapor phase reactions, it may be advantageous to dilute the hydrocarbon-halogen mixture. Such dilution facilitates the control of the reaction 7 since it prevents or decreases excessive decomposition, flashing of the mixture, and tar and,

carbon formation. Various inert diluents may be used. For example, carbon dioxide, nitrogen and helium, which may be employed individually or in combination with each other and/or with still other diluents, are representative examples of gaseous diluents which are particularly suitable for the vapor phase halo-substitution reactions. Obviously, the use or such diluent may be dispensed with, or still other inert diluents, whether gaseous or liquid, may be 'used.

As pointed out above, the presence of the free radicals formed by the decomposition or cleavage of the organic peroxides, allows th realization of the halo-substitution reaction at substantially lower temperatures than those which are necessary for effecting a substantial halo-substitution. by thermal, non-catalytic halogenation. Also, the use of the small percentages of the catalyst described herein increases the rate of halo-substitution, so that, under identical operating conditions, the halo-substitution in the presence of the organic peroxides will require a relatively shorter period of residence time as compared to that required for a thermal, non-catalytic halosubstitution reaction. Therefore, the present process allows greater space velocities to efiect the same conversion of the saturated organic compounds into their halo-substituted derivatives, thus increasing the effective capacity of any given reaction chamber. It is thus seen that the process of the present invention finds utility even when the halo-substitution reaction is effected at temperatures which are sufficient to activate the halogen and thus cause halo-substitution even in the absence of the catalyst.

We claim as our invention:

1. A process of halogenating a saturated aliphatic hydrocarbon which comprises reacting said hydrocarbon with a halogen selected from the group consisting of chlorine, bromine and iodine, in the vapor phase, at a temperature of below 200 C., and in the presence of ascaridole employed in an amount up to 5 mol per cent as calculated on the basis of the gaseous mixture subjected to the halogenation reaction.

2. The process according to claim 1, wherein chlorine is employed as the halogenating agent.

3. A process of halogenating a saturated aliphatic hydrocarbon which comprises reacting said hydrocarbon with a halogen selected from the group consisting of chlorine, bromine and iodine, in the liquid phase, at a temperature of below 200 C., and in'the presence of ascaridole employed in an amount up to 5 mol per cent as calculated on the basis of the mixture subjected to the halogenation reaction.

4. A process of halogenating a saturated aliphatic hydrocarbon which comprises reacting said hydrocarbon with a halogen selected from the group consisting of chlorine, bromine and iodine, at a temperature of below 200 C.,' and in the presence of small quantities of an organic peroxide which yields halogenation promoting free radicals under the operating conditions.

5. The process according to claim 4, wherein ascaridole is employed as'the organic peroxide which yields free radicals.

6. A process for the halogenation of a saturated aliphatic hydrocarbon which comprises mixing the hydrocarbon to be treated with a halogen selected from the group consisting of chlorine,

bromine and iodine, and effecting the reaction in the absence of actinic radiation and in the presence of a halogenation promoting catalyst comprising an organic peroxide which yields free radicals under the operating conditions.

7. A process {or the halogenation of a saturated alicyclic hydrocarbon which comprises reacting said hydrocarbon with a halogen selected from the group consisting of chlorine, bromine and,

halogenation promoting free radicals under the operating conditions.

9. A process for the halogenation of saturated hydrocarbons which comprises reacting the hydrocarbon with a. halogen selected from the group consisting of chlorine, bromine and iodine, in the absence of actinic radiation and in the presence of a halogenation promoting catalyst comprising an organic peroxide which yields free radicals under the operating conditions.-

10. A process of halogenating, via substitution, a saturated organic compound which comprises reacting said compound with a halogen selected from the group consisting of chlorine, bromine and iodine, at a temperature of below 200 Chand in the presence of an organic peroxide which yields halogenation promoting free radicals under the operating conditions.

11. A process of halogenating, via substitution, a saturated organic compound which comprises reacting said compound with a halogen selected from the group consisting of chlorine, bromine and iodine, in the absence of actinic radiation and in the presence of an organic peroxide which yields halogenation promoting free radicals under the operating conditions.

12. A process of halogenating, via substitution,

a saturated organic compound which comprises efiecting a reaction between said compound and a halogen selected from the group consisting of chlorine, bromine and iodine, at a temperature below that at which non-catalytic halogenation normally occurs to any appreciable extent, and in the presence of an organic peroxide which yields free radicals under the operating conditions.

13. A process for the halogenation, via substitution, of a saturated organic compound which comprises reacting said compound with a halogen selected from the group consisting of chlorine. bromine and iodine in the presence of an organic peroxide which yields free radicals under the operating conditions.

WILLIAM E. VAUGHAN. FREDERICK F. RUST. 

